Search
Effect of the Catalytic Center on the Electron Transfer Dynamics in Hydrogen-Evolving Ruthenium-Based Photocatalysts Investigated by Theoretical Calculations
Abstract
The light-induced relaxation pathways in the molecular photocatalyst [(tbbpy)2Ru(tpphz)PtCl2]2+ are investigated with time-dependent density functional theory calculations together with the Marcus theory of electron transfer (ET). The calculations show that metal (Ru) to ligand (tpphz) charge transfer (MLCT) triplet states are populated following an excitation in the longer wavelength range of the absorption spectrum, but that an ET toward the catalytic center (PtCl2) from these states is thermodynamically unfavorable, implying that charge separation can only occur via higher energy states in this system. Moreover, low-lying Pt-centered states can be populated and the calculations predict that they can form an excited state equilibrium with MLCT states localized on the tpphz ligand. A comparison with previously reported results for the photocatalyst [(tbbpy)2Ru- (tpphz)PdCl2]2+, based on a PdCl2 catalytic center, is provided in order to decipher the effect of the catalytic center on their respective photochemistry (Staniszewska, M.; Kupfer, S.; Guthmuller, J. Chem.Eur. J. 2018, 24, 11166−11176).
Citations
-
1 7
CrossRef
-
0
Web of Science
-
1 6
Scopus
Authors (3)
-
Stephan Kupfer
Cite as
Full text
- Publication version
- Accepted or Published Version
- DOI:
- Digital Object Identifier (open in new tab) 10.1021/acs.jpcc.9b03621
- License
- Copyright (2019 American Chemical Society)
Keywords
Details
- Category:
- Articles
- Type:
- artykuły w czasopismach
- Published in:
-
Journal of Physical Chemistry C
no. 123,
pages 16003 - 16013,
ISSN: 1932-7447 - Language:
- English
- Publication year:
- 2019
- Bibliographic description:
- Staniszewska M., Kupfer S., Guthmuller J.: Effect of the Catalytic Center on the Electron Transfer Dynamics in Hydrogen-Evolving Ruthenium-Based Photocatalysts Investigated by Theoretical Calculations// Journal of Physical Chemistry C -Vol. 123,iss. 26 (2019), s.16003-16013
- DOI:
- Digital Object Identifier (open in new tab) 10.1021/acs.jpcc.9b03621
- Sources of funding:
-
- Free publication
- Verified by:
- Gdańsk University of Technology
seen 143 times
Recommended for you
Ultrafast Intramolecular Relaxation and Wave-Packet Motion in a Ruthenium-Based Supramolecular Photocatalyst
- M. WäCHTLER,
- J. Guthmuller,
- S. Kupfer
- + 6 authors
Synthesis and hydrogen evolving catalysis of a panchromatic photochemical molecular device
- J. Habermehl,
- N. Djawed,
- M. Martynow
- + 4 authors
A Novel Ru(II) Polypyridine Black Dye Investigated by Resonance Raman Spectroscopy and TDDFT Calculations
- J. Guthmuller,
- S. Kupfer,
- M. Wachtler
- + 3 authors